CH628671A5 - Method for producing reactive dyes. - Google Patents

Description

628 671

2nd

PATENT CLAIMS I. Process for the preparation of dyes of the formula

F

9

X

1 \__

N SN

i ti

NH - C C - N

V

1

'Ro

The invention accordingly relates to a process for the preparation of dyes of the formula

F

, A

N

i

X

10th

(1),

II

1 \_

NH - C G - N

V

A

* R-

(1).

wherein Rt is hydrogen or a low molecular weight alkyl group, R2 is the remainder of a sulfo-containing azo dye, and Xj 15 and X2 is hydrogen or a sulfo group, and wherein the benzene ring A can also contain further substituents,

characterized in that an amine of the formula

(2),

wherein Xj and X2 is hydrogen or a sulfo group, condensed with 2,4,6-trifluoro-1,3,5-triazine, the resulting intermediate with a diaminobenzene compound of the formula wherein R] is hydrogen or a low molecular weight alkyl group, R2 is the rest of a sulfo group Azo dye, and X, and X2 is hydrogen or a sulfo group, and wherein the benzene ring A may contain further substituents, characterized in that an amine of the formula

(2),

wherein X1 and X2 is hydrogen or a sulfo group, condensed with 2,4,6-TrifIuor-l, 3,5-triazine, the resulting intermediate with a diaminobenzene compound of the formula

30th

HN

\

Ri

(3),

HN-

/ R.

R, '

\

(3),

R /

35

where R! Hydrogen or a low molecular weight alkyl group and R2 'is the remainder of a diazo component containing a diazotizable primary amino group, condenses, the secondary condensation product is diazotized and with a coupling component of the formula KH, wherein K is the remainder of a coupling component of the benzene or naphthalene series or the hetero -cyclic series is domes.

2. The method according to claim 1, characterized in that a 45 aminonaphtholsulfonic acid is used as the coupling component of the formula K-H.

3. The method according to claim 1, characterized in that a coupling component of the pyrazolone, 6-hydroxypyridone or the di- or triaminopyridine series is used as the coupling component of the formula K-H. 50

where R! Hydrogen or a low molecular weight alkyl group and R2 'is the remainder of a diazo component containing a diazotizable primary amino group, condenses, the secondary condensation product is diazotized and with a coupling component of the formula KH, where K is the remainder of a coupling component of the benzene or naphthalene series or the heterocyclic series is, couples.

In addition to the sulfo group and the radicals X, the phenyl nucleus À can also carry other substituents, e.g. Methyl or ethyl groups, methoxy or ethoxy groups, halogen atoms, such as e.g. Chlorine, and carboxylic acid groups.

If R2 'is an aryl radical without a dye character, this means in particular a benzene or naphthalene radical which bears those substituents which enable further diazotization, such as e.g. an amino group.

The following may be mentioned as amines of the formula (2): aniline-2-sulfonic acid, aniline-2,4- or -2,5-disulfonic acid.

The following may be mentioned as compounds of the formula (3):

The present invention relates to water-soluble, sulfo group-containing fluorotriazine reactive dyes which are substituted on the triazine ring by an ortho-sulfophenylamino radical. Dyes of this type have not been described to date, since the uniform condensation of ortho-sulfo-substituted amino nozo dyes causes difficulties because of the rapid hydrolysis of the trifluorotriazine.

It has now surprisingly been found that trifluorotriazine can be condensed in a simple manner and with almost quantitative yields with ortho-sulfo-substituted aniline derivatives without dye character, and that these condensation products can in turn be converted into valuable reactive dyes by further condensation, diazotization and / or coupling .

Diamines

1,3-phenylenediamine-4-sulfonic acid,

1,4-phenylenediamine-2-sulfonic acid, 55 2,4-diaminotoluene-5-sulfonic acid,

2,5-diaminotoluene-3-sulfonic acid. As an intermediate of the formula

60

65

H

Ä,

3rd

628 671

which can be converted into a dye by diazotization and coupling, e.g. called the following:

F

so3H

Suitable coupling components KH are, for example: 3-Kre-sol, phenol-4-sulfonic acid, β-naphthol, 2-naphthol-6- or -7-sulfonic acid, 2-naphthol-3,6- or -6,8-disulfonic acid, 1-naphthol-4-sulfonic acid, l-phenyl-3-methyl-5-pyrazolone, l- (4'-sulphophenyl) -3-methyl-5-pyrazo'ion, l- (2 ', 5 '-Dichlor-4'-sulfophenyl) -3-methyl-5-pyrazolone, 3-aminocarbonyI-4-methyl-6-hy-hydroxypyridone-2, l-ethyl-3-cyano- or -3-chloro- 4-methyl-6-hydroxypyridone-2, l-ethyl-3-sulfomethyl-4-methyl-6-hydroxy-pyridone-2,2,4,6-triamino-3-cyanopyridine, 2- (3'- Sulfophenylamino) -4,6-diamino-3-cyanopyridine, 2- (2'-hydroxyethylamino-no) -3-cyano-4-methyl-6-aminopyridine, 2,6-bis- (2'-hydroxy- ethylamino) -3-cyan-4-methylpyridine, 2-benzoylamino-5-naphthol-7-sulfonic acid, l-benzoylamino-8-naphthol-3,6- or -4,6-disulfonic acid, phenol, p-cresol , Acetoacetanilide and aceto-acet-2-methoxyaniline-5-sulfonic acid, l- (4'-sulfophenyl) -pyra-zolon- (5) -3-carboxylic acid, 3-methylpyrazolone- (5), 4-hydroxy-quinolone- (2), 8-acetylamino-l-naphthol-3-sulfonic acid, 2-aminone aphthaline-5,7-disulfonic acid, l-naphthol-4,6- or -4,7-disulfonic acid.

The dyes of the formula (1) and their dye intermediates are preferably prepared in aqueous solution or suspension, at low temperature and at a weakly acidic, neutral to weakly alkaline pH. The hydrogen fluoride liberated during the condensation is advantageously continuously neutralized by adding aqueous alkali metal hydroxides, carbonates or bicarbonates. The intermediate products containing a diazotizable amino group are usually diazotized by the action of nitrous acid in aqueous mineral acid solution at low temperature, and the coupling is carried out at weakly acidic, neutral to weakly alkaline pH values.

The dyes of the formula (1) are distinguished by a higher reactivity than those which do not contain a sulfo group ortho to the amino group on the triazine ring.

They are suitable for dyeing and printing a wide variety of materials, such as silk, leather, wool, superpolyamide fibers and superpolyurethanes, but especially cellulose-containing materials with a fibrous structure, such as linen, cellulose, regenerated cellulose and especially cotton. They are suitable both for the exhaust process and for dyeing according to the 5 pad dyeing process, according to which the goods are impregnated with aqueous and, if appropriate, also salt-containing dye solutions, and the dyes are fixed after an alkali treatment or in the presence of alkali, if appropriate with the action of heat.

They are also suitable for printing, especially on cotton, but also for printing nitrogen-containing fibers, e.g. of blended fabrics containing wool, silk or wool.

It is advisable to subject the dyeings and prints to a grandiose rinse with cold and hot water, if appropriate with the addition of a dispersing agent which promotes the diffusion of the unfixed portions.

In the examples below, the parts are parts by weight and the temperatures are given in degrees Celsius.

example

25.3 parts of l-aminobenzene-2,5-disulfonic acid are dissolved in 100 parts of water at pH 7. At 0 °, 13.5 parts of 2,4,6-trifluoro-l, 3,5-triazine are added dropwise within 15 minutes with thorough stirring. The pH value is kept at 5 to 6 by simultaneous dropwise addition of aqueous sodium bicarbonate solution. An aqueous solution of 21 parts of the sodium salt of 1,3-diamino-benzene-4-sulfonic acid is added to the solution of the monocondensate obtained, and condensation is carried out at 15 ° and a pH of 6.5 until no more diamine can be detected. The condensation product obtained, which still contains a diazotizable amino group, is now diazotized analogously to the instructions in Example 1. 40.5 parts of the disodium salt of l-acetylamino-8-hydroxynaphthalene-3,6-disulfonic acid are added to the solution of the diazo compound and the mixture is then coupled at pH 7 to 7.5. Evaporation of the entire reaction mixture gives a red dye powder which colors cotton in brilliant shades of red.

In a similar manner, further dyes according to the invention can be prepared if 2,4,6-trifluoro-1,3,5-triazine is analogous to the procedure described above, first with an aminobenzenesulfonic acid in column 2 and then with a diaminobenzenesulfonic acid in column 3 of the table below condensed. If the secondary reaction product obtained in this way is diazotized and combined with the coupling component listed in column 4, reactive dyes are obtained which dye the cellulose material in the tones indicated in column 5 in light and wet fastness.

No aminobenzenesulfonic acid diaminobenzenesulfonic acid coupling component

Color tone on cellulose

1-aminobenzene-2-sulfonic acid 1,4-diaminobenzene-2-

sulfonic acid

1-Amino-4-methylbenzene-2-sulfonic acid

1-Amino-3-methyl-benzene-6-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid do.

1 - (2 ', 5' -disulfophenyl) - reddish

3-methyl-pyrazolone- (5) yellow

1-ethyl-3-sulfomethyl-4-yellow methyl-6-hydroxypyridone- (2)

2-aminonaphthalene-5,7-di-orange sulfonic acid

1 - aminobenzene-2,4-disulphonic acid do.

1-Hydroxynaphthalene-4-sulfonic acid scarlet

1-amino-4-methoxy-benzene-2-sulfonic acid do.

2-hydroxynaphthalene-3,6-orange disulfonic acid

628 671

No aminobenzenesulfonic acid

6 l-Amino-4-carboxy-benzene-2-sulfonic acid

4th

Diaminobenzenesulfonic acid coupling component do.

2-sulfoacetylamino-5-hydroxynaphthalene-7 sulfonic acid

Color tone on cellulose orange

7 l-Amino-4-methoxy-do. benzene-2,5-disulfonic acid

8 l-aminobenzene-2,5-di-do. sulfonic acid

2-acetylamino-8-hydroxy-naphthalene-6-sulfonic acid l-benzoylamino-8-hydroxy-naphthalene-3,6-disulfonic acid yellowish red red bluish red

1-aminobenzene-2-sulfonic acid

1,3-diaminobenzene-4-sulfonic acid

HO

u — 0 SOjH

reddish blue

10 l-amino-4-chloro-benzene-2-sulfonic acid do.

blue

Dyeing Instructions I

2 parts of the dye obtained in Example 1 are dissolved in 100 parts of water with the addition of 0.5 part of sodium m-nitrobenzenesulfonate. A cotton fabric is impregnated with the solution obtained so that it increases by 75% in weight, and then dried.

Then the fabric is impregnated with a 20 ° warm solution containing 5 grams of sodium hydroxide and 300 grams of sodium chloride per liter, squeezed to 75% weight gain, the dye is dampened for 30 seconds at 100 to 101 °, rinsed, soaped in for a quarter of an hour a 0.3% boiling solution of an ion-free detergent, rinses and dries.

35

45

Staining instructions II

2 parts of the dye obtainable according to Example 1 are dissolved in 100 parts of water.

The solution is added to 1900 parts of cold water, 60 parts of sodium chloride are added and 100 parts of a cotton fabric are added to this dye bath.

The temperature is increased to 40 °, 40 parts of calcined soda and another 60 parts of sodium chloride being added after 30 minutes. The temperature is kept at 40 for 30 minutes and then the dye is soaped for 15 minutes in a 0.3% boiling solution of an ion-free detergent, rinsed and dried.

C.